Nu-(aminoalkyl)-nu, nu&#39;-alkyleneureas and methods of producing them



N=(AMINGALKYL)-N,N'-AELKYLENEUREAS AND METHUDS F PRQDUKCENG THEM Robert S. Yost, Oreland, Pa assignor to Robin & Haas Company, lihiiadelphia, Pa, in corporation at Delaware No Drawing. Application September 1955 Serial No. 533,511!

7Claims. crasseme where A is an alkylene group having 2 to 3 carbonatoms 3 of which at least two extendin a'chain between the adjoined N atoms, Z is an alkylene group having 2 to 18 carbon atoms of which at least two extend in a chain between the N atoms, R, when not directly attached to R, is selected from the group consisting of H, phenyl,

benzyl, cyclohexyl, and alkyl and alhenyl groups having from 1 to 18 carbon atoms, R, when not directly attached to R, is selected from the group consisting of phenyl, benzyl, cyclohexyl, and alkyl and alkenyl groups having from 1 to 18 carbon atoms, and R and R, when attached directly together, form a'heterocyclic ring with the adjoining N atom of theformula and are selected from the group consisting of the morpholinov residue =(CH CH O, the piperidino residue -(CH and the pyrrolidino residue (CI-l These compounds may be made by reacting a primary or secondary amine with certainnew compounds which I have recently discovered having the Formula II":

Where X is a halogen selected of chlorine and bromine.

Examples of amines of primary and secondary. type, which may be reacted with a compound of 'Formula'II to produce the compounds of the present invention, include: methyiamine, dimethylamine, ethylamine, diethy1- amine, propylamine, isopropylamine, n'-butylamine, di- (n-butyDarnine, sec-butylamine, di-(sec-butylya'mine, amylamine, hexylamine, cyclohexylamine, dicyclohexyh amine, phenylarnine, diphenylamine, benzylamine, di-

from the group consisting benzylamine, methylbenzylamine, methylphenylamine, e

methylethylamine, ethylb'enzylamine, n octylamine, di-' (n-octyl)amine, lauryiamine; Z-dodecenylamine, hexadecylamine, octadecylamine, ,di (octadecyl)amine, mor pholine, piperidine, pyrrolidine; j

The compounds of Formula IFmay 'be made in the.

, manner described and claimed'in' my'copen'ding application, derial No. 500,363, filed OITAPIil 8; 1955, and

10 I halide-and thecompoundlof Formula IV may be usedin 2' 7 involves. the reaction? of. thionyl halides. III .with a compound of Formula IV;

where. X, A-, andvZcare as. defined above. The thionyl approximately equimolar amounts. and the reaction is preferably, effected in-a solution. of the. compound of Formula lv, such as. in. chloroform. Preferably. the thionylhalide is. added gradually. For example, when the reaction involvesza batch containing about two moles:

of a. compoundofFormula IV, the thionyl halide may be added, over a period of two hours. Reaction islpreferably, efiect'ed at a temperature of to C. Advant ageously, it may be carried out with the solvent at reflux, in the' case of chloroform, refluxing occurring at a temperature of about 58 to 66 C. After completion of theaddition of the. thionyl halide, the solvent,

such as the chloroform,,may be gradually distilled while introducing, toluene until the temperature in the vessel reaches'about' to. 109 C. It is then refluxed for about 20 hours in the toluene. The product of Formula IIIisusually soluble'iir the hot toluene which is cooled to'about5' to 10 C or lower to precipitate ,the compound of Formula II. The precipitated productvmay then he'filteredand, ifldesired', washed with cold toluene. It 'is'therr'air-dried' or dried'under a vacuum at room temperature. Insteadiofchloroform, other solvents, such.

ascarbontetrachlaride and ethylene dichloride, may he used; andin'pla'ceof toluene, other non-polar. solvents,

- such as benzene, xylene, arms like may be used.

The compounds ofFormulalVmay be made invarious 'Ways described in a' copending application, Serial No; 348,105, filedApril 10, 1952, now P'atentNo. 2,727,- 019, in the hands of a common assignee. For example, as there disclosed, urea may becondensed with a following I HOCH CH NHCH CH NH hydroxyalkylaininoalkylamine; such as any one of. the

1 2,840,561 Patented June 24,1258

of the Formula The reaction with urea may be efiected by mixing one of the above hydroxy-diamines with an approximately equimolecular weight of urea and heating the mixture at sufficient temperature to evolve ammonia. Generally, temperatures may be between 200 to 210 C. Usually the reaction runs in two temperature ranges, initial evolution of ammonia occurring at 110 to 150 C., and the completion of the evolution of ammonia being effected at temperatures of 150 to 200 C.

The reaction of the primary or secondary amine with a compound of Formula II to produce the new compounds of Formula I may be efiectedwithout a solvent, but is preferably eifected in a solvent, such as benzene, toluene, xylenes, water, or alcohols, such as ethanol, isopropanol, butanol, and so on. Generally, from 2 to 3 moles of the amine is used to each mole of the compound of Formula II so that excess amine is available to take up the hydrogen chloride or hydrogen bromide liberated. Instead of having an excess of the amine' reactant to accept the hydrohalide developed, there may beused at least one equivalent of a tertiary amine, such as trimethylamine, triethylamine, or the like, or of an alkali metal carbonate, such as sodium or potassium carbonate or bicarbonate, the carbonates being particularly useful when a non-volatile amine reactant is involved, for each mole of the compound of Formula II reacted for the purpose of accepting the hydrohalide developed. The tempera: ture of reaction may'be from room temperature for a period of 24 to 48 hours or more up to about,200." C. for periods of 15 minutes or so. When a volatile amine is used, such as monomethylamine, an autoclave may-be employed to facilitate the retention of the amine .within the reaction medium at elevated temperatures. 3 When a volatile amine is used, as mentioned before,'a pressure of 20 to 100 pounds per square inch gage may be'developed, such as at a reaction temperature of 100 C. The product may be isolated by filtering off the hydrochloride salt or hydrobromide salt of the amine reactant when such salt is insoluble and leaving the salt of the product amine in solution. Then solvent is distilled oh? and the product is distilled at low pressures on the order of l to 2 mm. Hg. If no insoluble amine salt isproduced in the reaction, isolation may be efiected by the addition of an alkaline material, such as sodium methoxide, to precipitate sodium chloride or sodium bromide and liberate the free amines. The salt is then filtered off and the amines are fractionally distilled to produce the product.

Examples of the new compounds of Formula I include:

1- ,s-methylaminoethyl imidazolidinone-2; 1- fl-dimethylaminoethyl) -imidazolidinone-2; 1- (B-ethylaminoethyl imidazolidinone 2; 1 (B diethylaminoethyl imidazol idiuone-Z; lfl-diisopropylaminoethyl) imidazolidinone-2; 1-(18-butylarninoethyl)imidazolidinone-Z; l-(fl-octadecylaminoethyl imidazolidinone-Z; 1- (p-morpholinoethyl) imidazolidinone-Z; 1-(,B-piperidinoethyl)imidazolidinone- 2; 1 8 pyrrolidinoethyl)imidazolidinone 2; 1 ('y-dimethylaminopropyl)imidazolidinone 2; 1'- diethylaminopropyl)imidazolidinone-Z; 1 (B dimethylamindethyl)-5-methyl-imidazolidinone-2; l-(q-dimethylaminopropyl) S-rnethyl-imidazolidinone-Z; l- (4-dimethylaminobutyl)imidazolidinone-2; l-(-dimethylaminodecyl) imida zolidinone-2; 1- fi-ethylamino) decyl-S -methyl-imidazolidinone-Z; l-I( g-methylaminoethyl) tetrahydro -pyrimidinone-2; l-(B-diethylaminoethyl)-tetrahydro-pyrimidinone- 2; 1- it-dicyclohexylaminoethyl) -tetrahydro-pyrimidinone- 2; i ([3 ('isopropylamino)propyl)-tetrahydro-pyrimidinone-2; l-(j-butylaminopentyl)-tetrahydro-pyrimidinone- 2; l- 5 hexadecylaminopentyl -tetrahydro-pyrimidinone- 2; l-(,B-morpholinoethyl)-tetrahydro-pyrimidinone-2; and

l (,8 (methylbenzylamino)propyl) tetrahydro pyrim-' idinone-2.

Preferred compounds of the present invention are those of Formula I, in which A and Z are ethylene, R is hydro- F I s 4 gen or a lower alkyl of 1 to 4 carbon atoms, and R is a lower alkyl having 1 to 4 carbon atoms.

The compounds of the present invention having the structure of Formula I are generally high-boiling liquids to solids of various melting points. They are generally soluble in Water and alcohols, such as methanol, ethanol, and isopropanol when the carbon atom size of the substituents Z, R, and R is not excessively long, that is generally not over 4 to 6 carbon atoms in size. All of the compounds including both the lower and higher molecular weight compounds of Formula I are soluble in benzene, toluene. xylenes, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, and generally also in ethyl acetate, ether, acetone, dioxane, and the nitro-parafiins, including especially nitroethane.

The new compounds ofFo'rmula I are useful as corrosion inhibitors for automobile antifreezes. They are also useful corrosion inhibitors in steam generating systems for which purpose they may be introduced into the feed water for the boiler and may be selected to steam distill during operation of the boiler so as to protect the return lines. The new compounds may also be introduced as modifiers oi aminoplast types of thermosetting resin-forming condensates, such as those of urea-formaldehyde, melamine formaldehyde and the like. The modified aminoplasts may be used for increasing the Wet strength of paper, for the treatment of textiles, especially those of cellulosic types including cotton and rayon, to condition them for various purposes. For example, the compounds havinglong chain hydrophobic groups for the substituents R and R and also Z may be used to impart water-repellency and to serve as lubricants. Certain of the compounds having proper balance between hydrophobic and hydrophilic ends in the molecule show surface activity and may be used as dispersing agents and as detergent agents or auxiliaries. The incorporation of 1% H1870 of a compound of Formula I in spinning solutions of cellulose esters, such as cellulose acetate/in acetone, the percentage being based on the weight of. cellulose ester, serves to inhibit gas fading of the fibers, filaments, or other structures made from the solutions when they are dyed.

Those compounds of Formula I in which R is a hydrogen atom have two nitrogen atoms-carrying reactive hydrogen and are adapted to react with various agents and particularly aldehydes. Thus, they may be methylolated with formaldehyde and the. products thereby obtained serve to cross-link materials containing hydroxyl or primary or secondary amide or amino groups. For example, reaction of the methylolated compounds with nylon, wool, or casein fibers, or with cellulosic materials such as fibers, yarns, or fabrics of rayon or cotton serve to reduce shrinkage and imparts crease-resistance as well as reduced moisture pick-up or regain. The presence of the hydrogen atom on one of the ring nitrogen atoms and the presence of a single hydrogen atom on the side chain nitrogen prevents the production of trimers when the compounds of the present invention are reacted with formaldehyde, which trimers on subsequent reaction, as with the hydroxyl groups of cellulose, apparently form relatively unstable cross-links as compared to the crosslinks obtained with the dimethylol compounds, of the present invention.

7 A preferred group of the compounds of the present invention are those in which R is not hydrogen. Of this group, those in which R'and R are alkyl groups having 6 to 18 carbon atoms are useful as oil additives to lower the pour point, to reduce corrosion and to generally improve the oil characteristics, such as viscosity. and so on. The compounds in which R is other than hydrogen may be reacted with aldehydes and especially formaldehyde to produce derivatives which are capable of reaction with nylon, wool, .casein fibers and fabrics, or with cellulosic materials, such as cellophane, cotton, or rayon, to modify lhand, stiffness, Water-repellency and so on. Wa-

r 5., r ter-repellency may be best obtained, in this Way, when R and/or R and/or Z in the compounds of Formula I are of long carbon chain length, such as from 8. to 18 carbon atoms, the greatest *efiect being obtained when all three are of such long chain lengths.

The compounds of the present invention in which R is other than hydrogen are also highly useful for the production of quaternary ammonium compounds which serve as: agents for treating and conditioning textiles, including surface active agents for wetting and cleaning such textiles; lubricating and softening agents to be applied to various materials, especially of cellulosic type, such as fibers and yarns of cellulose esters, especially cellulose acetate, 'or of rayon, as well-as to films of regenerated cellulose; antistatic agentstfor application to articles made of hydrophobic materials, such as fibers, films, yarns, textile fabrics, and other shaped articles formed of vinyl resins, such as polyvinyl chloride, polyaeaeear vinylidene chloride, polyacrylonitrile, copolymers of.

vinyl chloride, vinylidenechloride, and acrylonitrile with each other or with other comonomers including vinyl pyridines, vinyl acetate, methyl acrylate, other acrylates or methacrylates, also nylons and polyesters, such as polyethylene terephthalate. These quaternary. ammonium compounds are readily made directly from a compound of Formula I in which R "is other than hydrogen by reacting it with an alkylating agent such as methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, substituted allyl chloride, e. g., dodecylallyl chloride, dodecenyl chlorides, alkylbenz'yl chlorides, e. g., octylbenzyl chlorides (from .diisobutylen'e), any chloromethylated aromatic-like compound, e. g., chlorobenzyl chloride, chloromethylated thiophene, chlorome'thylated furane, chloromethylated naphthalene, 'or corresponding bromides or iodides, e. g., phenoxyethyl'bromide, methyl iodide; dimethyl sulfate, dimethyl sulfite, dimethyl 'phosphite, ethylene oxide, propyleneoxide, styrene oxide, and butylene oxide. The quaternizationvmay be effected in a solvent, such as a lower alcohol, e. g., methanol, ethanol, isopropanol. Generally the .reaction may be effected at a temperature between 50 and -l20.- Q, preferably between 70 and '90'C-., and conveniently at the temperature of reflux or boiling-of the solventlused, The

product may be recovered by distilling ofithe solvent, at atmospheric pressure or in vacuo. The quaternaries can also be made by progressively alkylating a compound of Formula I in which R is hydrogen. v

All of the compounds of the present invention (Formula I) have been found to react with acetylene as disclosed in my copending application Serial No. 533,511, filed on even date herewith, wherein the new Vinyl derivatives obtained are claimed. It has been found that the presence of the hydrogen atom on.the ring nitrogen is essential for this purpose. In this connection, the compounds of the presentinvention in whichv R is other than hydrogen are preferred because of the wide range of copolymers that can be made from them, whereas the vinyl derivatives obtained-fromcompounds the same as those of Formula I herein except that one or both of R and R is or are hydrogen react in other ways, such as by a 1,4 addition mechanism or by aminolysis with many available monoethylenically unsaturated monomers, such as the esters, amides, acids, and nitriles of unsaturated acids, including acrylic, methacrylic, etc. acids.

In the following examples, which are illustrative of the invention, the parts given are by weight unless otherwise indicated.

Example A In a reaction vessel fitted with mechanical stirrer, thermometer, dropping funnel and reflux condenser are placed 260 parts of N-(B-hydroxyethyl)N,N'-ethyleneurea (obtained from the condensation of urea with the compound of Formula V(a) above) and 600 parts of anhydrous chloroform. The mixture is heated to reflux for the imidazolidinone of part (a).

and 238 parts'of purified thionyl chloride is added drop- Wise over a period of two hours. Reflux is maintained by the heat of reaction for most of this period. The chloroform is then distilled out of the mixture while 348 parts of anhydrous toluene is added at approximately the same rate at which the chloroform is distilled. Distillation is continued until the vapor temperature reaches .C. The mixture is refluxed for sixteen hours and then is chilled in an ice bath. The product precipitates and is filtered, washed with cold toluene, and dried at 60 C. to give 268 parts (a 90% yield of N-(B-chloroethyl)-N,N-ethyleneurea, M. P. 81.5 to 82 C. One recrystallization from toluene gives a colorless,.crystalline product melting at 84.0 to 85.0 C.

Analysis. Calculated for C H ON Cl: C, 40.41%; H, 6.11%; N, 18.86%; Cl, 23.86%. Found: C, 40.62%; H, 6.05%; N, 18.90%; Cl, 23.26%.

Example B The procedure of Example A is repeated substituting 316 parts of N-('y-hydroxypropyl)-N,N'-trimethyleneurea for the urea derivative there used. -N-('y-chloropropyl) N,N'-trimethyleneurea is the product obtained.

Example C An 88% yield of l-( 8-chloropropyl)-S-methyl-imidazolidinone-Z is obtained by repeating the process of Example A substituting 316 parts of l-(p-hydroxypropyn- S-methyl-imidazolidinone-Z for the urea derivative therein used.

Example D Q The following chloro'alkyl cyclic ureas are obtained by repeating the process of Example A with substitution for the hydroxyalkylurea used therein an equivalent molar quantity of the hydroxyalkyl cyclic urea obtained by condensation of urea with .the N-hydroxyalkylalkylenediamine of the formula given after the name of the product compound:

(a) 1- (p-chloroethyl)-tetrahydro-pyrimidinone-2 (from (b) 1 7 chloropropyl) 5 methyl-imidazolidinone (a) A stainless-steel autoclave is charged with 89 parts of l-(B-chloroethyl)-imiclazolidinone-2, 530 parts of henzene, and 81 parts of liquid anhydrous dimethylamine. The autoclave is sealed and the reaction mixture is stirred and heated at l00l05 C. for six hours during which time thepressure reaches a maximum of 40 p. s. i. and then drops so that, at the end of the heating period, the pressure is22 p. s. i. The reaction mixture is filtered to remove dimethylamine hydrochloride (47 parts) after which the filtrate is concentrated under reduced pressure. The product is distilled to yield 74 parts of l-(fi-dimethylaminoethyl)-imidazolidinone-2 boiling in the range 146 C. at 1 mm. of mercury. The product crystallizes on standing at room temperature. Melting point (crude): 5153-C. i

A sample of the product is converted to tliehydrochloride by precipitation from methanol with anhydrous hydrogen chloride. The salt after recrystallization from methanol melts at 202.5-203.0 C.

Analysis.-Calculated for C H ON Cl: Cl, 18.3%. Found: Cl, 18.0%.

(b) The procedure of part (a) is repeated substituting 106 parts of N-('y-chloro-propyl) N,N-trimethyleneurea There is obtained a solid product, l-('y-dimethylaminopropyl)-tetrahydropyrimidinone-Z.

i (c) The solid product, l-( -dimethylaminopropyl)-5- methyl-imidazolidinone-Z is obtained by repeating part (a) substituting for the imidazolidinone there used 106 parts of l(' -chloropropyl)-5-methylirnidazolidinone-Z. The products of parts (a), (b), and (c) are corrosion inhibitors useful in glycol antifreezes for automobiles at concentrations of 0.1 to 1.5 by Weight of the solution.

Example 2 (a) The procedure of Example 1(a) is repeated in a glass vessel equipped with an agitator and reflux condenser, the amine being replaced with 110 parts of dicyclohexylamine and 50 parts of potassium carbonate. The solid product is l-(,8-dicyclohexylaminoethyl)-imidazolidinone-2.

(b) Similarly 1-(,B-diocetadecylaminoethyl)-imidazolidinone-2 isobtained when the 110 parts of dicyclchexyl amine is replaced With 312 parts of dioctadecylamine.

By proceeding in part (a) but replacing the amine with 77.4 parts of dibutylamine and the imidazolidinone with 165 parts of l-(fl-chlorodecyl)--methyl-imidazolidinone (of Example D(e)), a solid product consisting of 1-( li-dibutylaminodecyl) -5-methyl-imidazolidinone-2 is obtained.

(d) Part (c) is repeated except that the imidaznlidinone is replaced with 1-(lO-chlorodecyl)-imidazolidinone-2 (of Example D(d)) and l-(IO-dibutylaminodecyl)-imidazolidinone-2 is obtained.

The products of parts (a) through (a') hereof are useful as water-repellent coating materials. Application to leather by rubbing or by aqueous emulsions serves to render the leather highly Water-repellent.

Example 3 (a) Thereare charged to a reaction vessel 148.5 parts of l-(fl-chloroethyl)-imidazolidinone-2 and 775 parts of 40% aqueous monomethylamine. The mixture is stirred at room temperature for thirty hours. At the end of this period, a titration for chloride ion shows the reaction to be essentially complete. After adding 40 parts of sodium hydroxidedissolved in about 60 parts of. Water, the water in the mixture is removed by distillation in vacuo. When virtually all of the water is distilled, 300 parts of benzene is added and the mixture is distilled until the distillate appears to contain no Water. The resulting mixture is filtered to remove sodium chloride (59 parts), the filtrate is concentrated in vacuo, and the residue is distilled to yield a product consisting of 98.5 parts of l-(fl-methylamin-oethyl)-imidazolidinone-2 boiling at 145150 C. at 0.5 mm. of mercury.

A sample of the product is converted to the hydrochloride by precipitation from methanol with anhydrous hydrogen chloride. The salt is recrystallized from a water-isopropanol mixture to give the purified product melting at 194.0-194.5 C.

An. 1ly5is.-Calculated for C H ON CI: Cl, 19.7%. Found: Cl, 19.5%. p

(b) The procedure of part (a) is repeated, replacing the imidazolidinone with 1-(B-chloroethyl)-tetrahydropyrimidinone-2. The solid product obtained is I-(B' methylaminoethyl)-tetrahydropyrimidinone-2.

When 1% by weight of the compounds of parts (a) and (b) are introduced intoboiler fcedwater, corrosio in the return lines reduced considerably.

Example 4 where A is an alkylene group having 2 to 3 carbon atoms of which at least two extend in a chain between the adjoined N atoms,.Z is an alkylene group having 2 to 18 carbon atoms of' which at least two extend in a chain between the N and X atoms, R is selectedfrom the group consisting of H, cyclohexyl, and alkyl groups having from -1 to 18 carbon atoms, R is. selectedfrom the group consisting of cyclohexyl" and alkyl groups having from 1 to 8 carbon atoms, and X is a halogen selected from the group consisting of chlorine and bromine; and recovering an N-(aminoalkyl) -N,N'-alkyleneurea from the reaction medium. v

2. A process as defined in claim 1 in which the time of reaction is from 15, minutes at the higher portion of the temperature range to'24 to 48 hours or so at the lower. portion thereof. 7

3. A process as defined in claim 1 inwhich the reaction is efiec'ted while'the reactants are in solution in an organic solv'entand excess amine is used.

4. A process. as defined in claim 3 in which the solvent used'is an aromatic hydrocarbonsolvent selected from the group consisting or benzene, toluene, and xylene.

5. A process as defined in claimv 3 in which the solvent used is an alcohol.

.6. A process as defined in claim 3 in which an aqueous solvent is used as the reaction medium.

7. A process as defined in claim 1 in which the reaction is efiected While the reactants are in solution in an organic solvent anda tertiary amine is used to take up the hydrohalide liberated by the reaction. 7

Refe rencjes'Citetl in the file of this patent UNITED STATES PATENTS 2,613,212 Hurwitzet a1. Oct. 7, 1952 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,840,561 June 24, 1958 Robert S, Yos'b Column 8, lines 32 and 33, claim 1, for "alkyl groups having from l to 8 carbon atoms, read alkyl groups having from 1 to 18 atemsw Signed and sealed this 19th day of August 1958,

Attest:

KARL Ha AFLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents 5 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,840,561 June 24, 1958 Robert S 9 Yost Column 8, lin's 32 and 33, claim 1, for

"alkyl groups having from 1 to 8 oarbon atoms, read alkyl groups havin g from 1 to 18 atelmsyu-h Signed and sealed this 19th day of August 1958 (SEAL) Attest:

KARL H AXLINE I ROBERT C. WATSON Attesting Oflicer Commissioner of Patents 

1. A METHOD WHICH COMPRISES REACTING AT A TEMPERATURE FROM ROOM TEMPERATURE TO 200*C. AMINE OF THE FORMULA HNRR'' WITH A COMPOUND OF THE FORMULA 